JPH0732310B2 - Method for manufacturing multilayer electronic circuit - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method of making a multilayer electronic circuit using a thick film paste.

[0002]

BACKGROUND OF THE INVENTION Multilayer structures are becoming increasingly complex for hybrid circuit manufacturers, and as the need for lower cost, higher wiring density circuits increases,
It is becoming more and more of a concern. Improvements in multilayer technology are important to meet these increasing demands.

There are several drivers in the market. For example, lower costs are important, which means a transition to pure silver, platinum / silver or copper metallurgy versus traditional gold or palladium / silver. Processing costs are equally important to circuit manufacturers, thus minimizing the number of printing and firing steps to reduce final circuit costs.

Narrower wiring intervals are also needed to promote miniaturization. Higher conductivity conductors are particularly useful for reducing wiring width. Fortunately, this need is consistent with the trend towards silver or copper metallization.

Higher reliability dielectric layers are necessary as the number of conductor crossovers in a circuit increases, especially when using pure silver or copper conductors. For screen printing applications, there is an ever increasing desire among customers to have three or two printing steps for the dielectric and two or one baking step to save processing costs. This trend has resulted in the development of more reliable crystallized glass systems. After additional firing, crystallized glass is much more stable after firing than standard lead borosilicate filled systems because the crystallization prevents further glass softening and flow. However, the same level of reliability and stability of this dielectric makes bonding standard thick film conductors to the substrate more difficult. When the conductor is fired on a previously fired dielectric, the aged adhesion usually deteriorates. This is because the crystallized dielectric is stable and the glass and flux in the conductor do not react well with the crystallized glass below.

[0006]

SUMMARY OF THE INVENTION (1) At least 25% by weight of SiO ₂ on an exposed surface of a substrate consisting of a plurality of alternating layers of inorganic dielectric material and layers of thick film conductors.
A layer of a thick film dielectric paste containing finely divided particles of amorphous glass, which contains, and has a softening point below the maximum firing temperature of step (3) below, (2) step (1) A thick film dielectric layer of (a) Ag, a mixture of an alloy of Ag and a small amount of Pd and / or Pt, and a mixture thereof;
Silver-containing particles having a maximum particle size of 20 microns and a surface area of at least 0.1 m ² / g; (b) PbO, B ₂ O ₃ , Si
At least two metal oxides selected from O ₂ and Bi ₂ O ₃ and up to 45% by weight of a glass modifier selected from oxides of alkali metals, alkaline earth metals, transition metals and mixtures thereof, An amorphous glass binder having a dilatometer softening point of 150 to 800 ° C.,
(C) Apply a patterned layer of thick film conductor paste containing fine particles of an anti-sintering agent selected from oxides of ruthenium and rhodium, mixtures thereof and precursors, provided that conductive metal is used. The amount of the sintering inhibitor with respect to the amount of is included within the range connecting points A to D in FIG. 1, and all of (a), (b) and (c) are dispersed in an organic medium; and (3) A layer to which the thick film dielectric paste and the thick film conductive paste are applied is co-fired with air to volatilize the organic medium from both layers, soften the glass binder and sinter the metal particles in the thick film conductor layer, And a method of manufacturing a multilayer electronic circuit comprising successive steps of densifying glass in a thick film dielectric layer.

BRIEF DESCRIPTION OF THE DRAWINGS The drawing is a graph showing the ratio of the sintering inhibitor required for the silver-containing conductive metal in the thick film conductive layer.

DETAILED DESCRIPTION OF THE INVENTION Broadly speaking, the present invention relates to a method of developing a technique for improving the aging adhesion of conductors to a dielectric layer. It is suitable for both glassy and glass-filled dielectric systems, as well as glass crystallization systems and glass-filled crystallization systems. In particular, it is useful for crystallization and filled crystallization systems because it is difficult to bond the conductor to the crystallized glass layer. The method involves firing a conductor on the dielectric prior to fully crystallizing the dielectric. It also means first firing the dielectric at a lower temperature, below its crystallization point, and then printing the conductor. However, it is particularly useful when printing conductors directly onto a printed dielectric with the dielectric in its green state. Therefore, the conductor and dielectric are fired together. This co-firing allows the conductor and dielectric glasses to flow together below the crystallization point of the dielectric to form a good bond. After bond formation, crystallization occurs at the peak firing temperature, effectively stopping the reaction.

In a ceramic-filled glass dielectric system, little crystallization occurs at peak firing temperatures. In this case, co-firing allows good bonding between the conductor and the dielectric layer during the co-firing process. Crystallization is not necessary for binding. However, co-firing is particularly useful for crystallization systems, as described below.

Co-firing the top conductor with the dielectric provides other benefits. Reduce the number of firing steps and lower the manufacturing cost of the final circuit. In particular, the need for belt furnaces by circuit makers is reduced, and capital expenditure is reduced. Also, the line resolution of the upper layer conductor is significantly improved when printing on a printed dielectric or green tape. This improved resolution is due to the rapid flow of solvent from the conductor into the dielectric layer, which causes localized viscosity in the conductor and prevents spread. Printing on glassy surfaces is more difficult as conductors tend to spread more on smooth surfaces. Typically, the upper conductor is printed continuously on the fired dielectric or cofired tape structure, which reduces line resolution.

Therefore, simultaneous firing of the upper conductor and the unfired dielectric has the following advantages. That is, improved bonding of conductors to dielectrics, especially crystallized dielectric chemicals, improved line clarity of upper layer conductors, and reduced manufacturing costs due to fewer firing steps.

The present invention is concerned with providing a secure bond between a soldered conductor layer and an adjacent dielectric underlayer.
This bond is designed to reduce the penetration of tin metal from the solder and still retain high adhesion. In order to form this bond more effectively, it is preferable to co-fire the conductor and the dielectric composition. However, this bond is not really related to the features of the circuit and the underlying substrate.
Thus, the top dielectric layer may be on a wide variety of substrates, for example (1) directly on an alumina substrate, (2) on a layer of alternating prefired conductor and / or dielectric layers, and ( 3) Can be applied on alternating layers of pre-dried and fired conductor and / or dielectric layers. Therefore, the composition was tested by screen printing the dielectric layer directly on the alumina substrate in the examples below,
The structure of the substrate is exemplary of the many methods that can be applied, and was chosen merely to simplify the test method.

Silver-Containing Conductor The present invention is particularly useful for the application of silver-containing thick film pastes, ie pastes in which the conductive metal is silver or an alloy of silver and a small amount (up to 35 mol%) of metals such as platinum and palladium. .

The maximum particle size of the silver-containing conductor phase should be less than 20 microns and preferably 10 microns or less. In addition, the conductor phase particle tap density should be at least 2 g / cc and preferably 3 g / cc to ensure film uniformity and improve shrinkage consistent with the underlying substrate.
And higher. The average surface area of the electrically conductive particles should be in the range of 0.1 to ³ m ² / g and preferably 0.2 to ² m ² / g.

Inorganic Binder The inorganic binder for thick film conductor paste is 150 to 800 ° C.
It must be a low softening point glass with a dilatomer softening point of. In particular, the softening point of the glass is such that it undergoes liquid phase sintering, ie it should start flowing during the co-firing before the sintering and densification of the conductive metal component is complete. Moreover, the inorganic binder must begin to flow during the sintering process before any crystallization occurs if the dielectric layer is crystalline. The softening point of glass is 2
It is preferably in the range of 00 to 600 ° C. The surface area of the conductive metal particles is 0.1 to ³ m ² / g and preferably 0.2.
It is preferably in the range of ˜2 m ² / g.

A wide range of glass compositions can be used as inorganic binders for thick film conductors as long as they meet the above criteria. In particular, lead and bismuth amorphous silicates, borosilicates and borates have been combined with up to 50% by weight of glass modifiers such as alkali metal oxides, alkaline earth metal oxides and transition metal oxides. It has been found to be particularly suitable if. Mixtures of these components and precursors can be used as well.

Optionally, the binder component can also contain auxiliary fluxing agents such as Bi ₂ O ₃ and PbO.

[0018]Sintering inhibitor Used as a sintering inhibitor for conductive metals in the present invention
Possible materials are rhodium (Rh) and ruthenium (R)
u) Oxides and their metal oxides under firing conditions
Rhodium-based compounds and ruthenium-based compounds
is there. Such materials may be in granular form or in organic media.
It can be in the form of an organometallic compound that is soluble.
For example, suitable Ru-based materials are Ru metal, RuO.₂,
Ru-based pyrochlore compounds such as bismuth ruthenate
Lead and copper bismuth ruthenate, resin acid Ru and their
Including a mixture. Suitable Rh-containing materials include Rh metal, Rh
O ₂, Rh₂O₃, Resin acids Rh and mixtures thereof
It The substantial criterion for both types of materials is that they are Rh or
Are Ru oxides, or they are air-baked to which they are applied.
Being a precursor of these oxides under synthetic conditions
It

The preferred sintering additive materials for use in the present invention are RuO ₂ , copper bismuth ruthenate and resin acid Rh.
The use of particulate sintering inhibitors as well as soluble organometallic sintering inhibitors is illustrated in the examples. However, it should be recognized that this inhibitor can also be present in the form of a coating on the conductive metal particles. Such coatings consist of dispersing conductive metal particles in a solution of a metal resinate of a sintering inhibitor, removing most of the liquid from the dispersion, and then drying the particles to form an oxide coating. It can be manufactured.

Organic Medium Inorganic particles are mixed with a substantially inert liquid medium (vehicle) by mechanical agitation (eg, on a roll mill) to form a paste-like composition having a consistency and rheology suitable for screen printing. This is printed as a "thick film" on a conventional dielectric substrate by conventional methods.

Any inert liquid can be used as the vehicle. Various organic liquids, with or without the addition of thickeners and / or stabilizers and / or other common additives, can be used as vehicles. Examples of organic liquids which can be used are aliphatic alcohols, esters of such alcohols such as acetates and propionates, terpenes such as pine oil, terpineol, resins such as solutions of polymethacrylates of lower alcohols and solvents such as ethyl cellulose in pine oil. And monobutyl ether of ethylene glycol monoacetate. Preferred vehicles are ethyl cellulose and β-
Based on terpineol. The vehicle, after being applied to the substrate, may contain a volatile liquid to promote fast cure.

The ratio of dispersion vehicle to solids can vary considerably, and will depend on the method to which the dispersion is applied and the type of vehicle used. Usually the dispersion is complementary 60-90% to achieve good coverage.
Solids and 40-10% vehicle. Of course, the composition according to the invention can also be modified by adding other materials which do not affect its advantageous characteristics. Such formulations are well known in the art.

The paste is conveniently manufactured on a three roll mill. Paste viscosities are typically within the following ranges when measured with a Brookfield HBT viscometer at low, medium and high shear rates.

Shear rate (sec ^-1 ) Viscosity (Pa, s) 0.2 100-5000 300-2000 preferred 600-1500 most preferred 4 40-400 100-250 preferred 120-200 most preferred 40 10-150 25-120 preferred 50-100 Most preferred The amount of vehicle used is determined by the final desired formulation viscosity.

[0025] In the production of the composition of the formulation and application present invention, the particulate inorganic solids are mixed with the organic carrier and a suitable device for example to form a suspension by dispersing a three-roll mill, the viscosity is 4 sec ^- A shear rate of ¹ gives a composition of about 100-250 Pascal seconds.

In the following examples, compounding is carried out by the following method.

The components of the paste, minus about 5% of the organic components, corresponding to about 5% by weight, are weighed and placed together in a container. The ingredients are then mixed vigorously to form a uniform blend and the blend is then passed through a disperser, such as a three-roll mill, to obtain a good particle dispersion. A Hegman gauge is used to measure the dispersion of paste particles. This device consists of a groove in a steel block that is 25 μm (1 mil) deep at one end and ramps up to a depth of 0 ″ at the other end. Use a blade to paste along the length of the groove. If the diameter of the mass is larger than the depth of the passage, scratches will appear in the groove.If the dispersion is well done, a fourth scratch point of typically 10 to 18 will be obtained. The points not covered by the dispersed paste are typically 3 to 8. A fourth scratch point of> 20 μm is measured, and a “half groove” of> 10 μm is measured as a dispersed suspension. Indicates insufficient liquid.

The remainder consisting of 5% of the organic component of the paste is then added and the viscosity of the fully compounded resin content is adjusted to 140-200 Pa.s at a shear rate of 4 sec ^-1 . The composition is then applied to the dried green dielectric layer, usually by screen printing, to a wet thickness of about 30-80 microns, preferably 35-70 microns, and most preferably 40-50 microns. The electrode composition of the present invention is applied to the dielectric layer by an automatic printer or a manual printer, preferably 20 by a conventional method.
It can be printed with an automatic screen stencil method using a 0-325 mesh screen. The printed pattern is then heated to below 200 ° C., about 150 before firing.
Dry at 5 ° C for about 5-15 minutes. Firing to sinter both the inorganic binder and the finely divided particles of metal burns the organic material in a well-ventilated belt conveyor furnace at about 300-600 ° C, with a maximum temperature period of about 700-1000 ° C for about Performed by providing a temperature profile that lasts 5 to 15 minutes, followed by controlled cooling cycles to prevent crushing of the substrate that can result from excessive sintering, undesired chemical reactions at intermediate temperatures or premature cooling. Is preferred. The whole firing process reaches about 1 hour, of which 20 ~
Reached the firing temperature in 25 minutes, and kept at the firing temperature for about 10 minutes,
And it is preferable to cool for 20 to 25 minutes. In some cases, a total cycle time of 30 minutes or less can be used.

[0029]

EXAMPLE A standard 1 ″ × 1 ″ Du Pont adhesive pattern was used for this study (Du Pont Technical Service Monogr
See C-7 and C-8 in aphs). It consists of a 2mm x 2mm bond pad and a 0.5mm x 100mm serpentine wire. After firing, solder leaching resistance was measured by the number of 10 seconds immersions in a fired layer resistant to 62/36/2 Sn / Pb / Ag solder at 230 ° C before the serpentine line showed discontinuity. A mildly active fluxing agent such as Alpha 611 was used. The destruction of the solder on the serpentine wire is either due to the leaching of metal into the solder reservoir or the dewetting of the serpentine wire by the solder.

Aging adhesion measurements were made on a 2 mm square pad,
Pre-tinned 20 gauge wire, 62/36/2
Of solder and mildly active Alpha 611 flux. Aging was performed at 150 ° C. for 1000 hours. Parts are automatic Instron ^R tensile tester, standard 90
Pulled using the ° peel orientation. The pull rate (crosshead speed) was 0.5 inches / minute.

The fired thickness of these examples was 10-12 microns. The parts were fired twice using a 850 ° C., 30 minute distribution.

The composition of the glass frit used in the conductors of this study, including the frit dilatometer softening point, is shown in Table 1. Table 2 shows the properties of the silver powder used in the conductor example.
Table 3 shows the composition of the dielectric glass. The composition of the dielectric paste is shown in Table 4, and the conductor formulations and test data are shown in Tables 5, 6 and 7.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4] Dielectrics S-V had the above-listed ratios of inorganic compounds and were formulated to be about 76 wt% solids in the paste. The balance (about 24% by weight) was the organic medium. Dielectrics W, X and Y are commercially available thick film pastes, QS4
82 is Du Pont's crystallized dielectric thick film paste, AP55
76 is the crystallized dielectric thick film paste of Asahi Glass and 5704 is the glass filled dielectric thick film paste of Du Pont.

[0037]

[Table 5]

[0038]

[Table 6]

[0039]

[Table 7]

It is typically more difficult to bond to crystallized glass than to amorphous glass dielectrics. This is about 5
This is especially the case for crystallized dielectrics with reduced silica content below 0% SiO ₂ . In Example 1, the conductor is formulated with silver powder, low softening point glass frit, and bismuth oxide. Aging adhesion is very low when firing separately crystallized crystallized dielectrics, and also very low when co-firing such dielectrics.

Significantly improved aging adhesion is obtained in Example 2 where the composition includes a RuO ₂ sintering inhibitor and the conductor and dielectric are co-fired. The same glass system as in Example 1 is used. The RuO ₂ precursor was prepared in Example 3
Ruthenium resinate used in. This shows that the improved effect of co-firing aging adhesion is obtained from the resinate precursor. Long-term aging adhesion is 20N
Although the total Ru content is not very high, the addition of ruthenium resinate further improves aging adhesion. In Example 4, ruthenium is present as the pyrochlore compound copper bismuth ruthenate. It is again worth noting that aging adhesion by co-firing is significantly improved over sequential firing of conductor and dielectric.

It is also observed from Examples 2-4 that the solder leaching resistance is improved. The addition of Ru noble metal has the additional advantage of improving solder leaching resistance. Because its addition reduces the solubility of silver, and its addition makes it possible to obtain a suitable aging bond using lower glass levels in the conductor formulation. High glass levels of silver compositions are known to reduce solderability and solder leaching resistance due to poor wetting.

The sintering inhibitor can be based on rhodium as well as ruthenium as shown in Example 5 using rhodium resinate. In either case, the rhodium or ruthenium dispersion is likely to become a noble metal oxide dispersion during firing, which hinders the sintering of silver particles and allows a larger silver / glass contact area after the firing step. Which improves the bond.

Example 6 Using Both Rhodium Resinate and Copper Bismuth Ruthenate for Both Rhodium and Ruthenium
It can be used together as a sintering inhibitor as shown in FIG. Similar improvements are observed in co-firing aged adhesion vs. sequential firing adhesion.

The present method of formulating with low softening point glass and ruthenium- or rhodium-based sintering inhibitors is particularly useful for pure silver compositions, which have high levels of glass in pure silver paste. This is because it is difficult to use a binder because it significantly deteriorates the solderability. However, this method is not limited to silver compositions. The silver / palladium formulation is disclosed in Example 4, while the silver / platinum composition is disclosed in Example 7, both of which show improved performance. Similar behavior is expected in gold and gold alloy systems.

In general, the best conductor glass compositions for the co-firing method are low softening point glasses based on Bi, Pb, B, and / or Si. Examples of lead borosilicate glass, bismuth lead borosilicate glass, lead bismuth silicate glass, and lead bismuth borate glass are found in Examples 1-7 above. The bismuth borate composition is Example 8
Shown in. Further, these glasses can be blended as shown in Example 7. The low softening point is useful for allowing the dielectric to interact with the dielectric glass before it crystallizes and ages. As Example 9 using a high silica modified lead borosilicate frit shows, a relatively high softening point conductor glass is undesirable. The conductor glass frit has a dilatometer softening point above about 600 ° C. and co-fired aging adhesion improved to 16 N, but not as high as the 20-30 N level of many other examples. In Example 10, a low softening point zinc-lead borosilicate frit was used. However, heavy Zn
With the addition of O, the glass composition was far from the claimed components of the invention, and co-fired aging adhesion was very low.

The upper limit of the glass softening point of the conductor is about 800 ° C., but the preferable upper limit is 600 ° C. No lower limit was found in this study, but a glass composition of preferred components with a dilatometer softening point below 300 ° C. was used (see Table 2).

Bismuth oxide is almost always present in solderable silver compositions because of its well known benefits of improving solderability. Bismuth oxide can be present in the glass or glasses containing bismuth or can be added separately to the conductor formulation. In Examples 3 to 8 it is present in the glass frit, in Examples 1 and 2 it is added separately as the bismuth oxide phase and in Examples 9, 11 and 12 it is added separately as the bismuth resinate. However, it is not necessary to use bismuth oxide in the formulation (in glass or as a separate additive) to apply the co-firing method. Practical bismuth oxide free formulations require a minimum amount of glass frit to obtain proper solderability.

The co-firing method and conductor formulation method are not limited to a limited variety of dielectric compositions. Several dielectric examples are used in Examples 1-12, all of which are described in more detail in pending US patent applications 07/653872 and 07/653874 filed February 8, 1991. ing. They use crystallized glass, or crystallized glass and ceramic-filled particles. Commercially available crystallized thick film composition QS482 (Du Pont) and AP557
The use of 6 (Asahi Glass) is also shown in Examples 13 and 14.
The co-firing method was useful to impart high bond strength after aging using the conductor composition of the present application.

As mentioned above, the co-firing method is particularly useful when used with a crystallized dielectric composition. However, it can also be used with glass compositions or glass-fill compositions which do not crystallize clearly as shown in Example 15 where the dielectric is the commercial product 5704 (Du Pont). In this example, the conductor composition provides both good co-firing and aging adhesion as well as good sequential firing and aging adhesion for a minimum amount of dielectric crystallization.

The co-firing method requires that the conductor have minimal shrinkage during firing to avoid separation from the dielectric. This phenomenon is well known in the field of multilayer capacitors, where the electrodes are co-fired with the dielectric layer. This shrinkage can be minimized using sintering inhibitors such as the ruthenium- or rhodium-based materials mentioned above.
Also, the metal powder has a great influence on the shrinkage. The powder surface area is the driving force for sintering, so low surface area powders are preferred. A practical lower limit for silver is about 0.1 m ² / g, below which the powders are typically too coarse to provide acceptable surface aesthetics for microcircuit applications. Excessive shrinkage above about 3 m ² / g results in extensive detachment and curl from the dielectric. In Example 16, some curl was observed after co-firing, and the co-firing method could not be used.

Another silver powder parameter that affects separation from the dielectric during co-firing is its tap bulk density. Generally, the higher the tap density, the better the fill in the dry film, and thus less shrinkage is needed to achieve the final desired density. Therefore, the higher the tap density, the better for co-firing applications. The actual lower limit is 0.7 g / cc, but the preferred range is above 2 g / cc. The glossaries QS482 and 5704 are E. I. du Pont de
Nemours & Co. It is the trade name of the thick film dielectric paste manufactured by. AP 5576 is Asahi Glass Compa
It is a trade name of a crystalline thick film dielectric paste manufactured by NY. Bismuth resinate is a product of Mooney Chemicals,
Inc. Is a trade name of bismuth-2-ethylhexoate containing 30% Bi. # 8826 is Eng of rhodium resinate containing 10% Rh
elhard Corp. This is the product name of the product. A2575 is En of ruthenium resinate containing 24% Ru
gelhard Corp. This is the product name of the product. Pigment # 211 is a The Chromium Cobalt Aluminate The Sheppard Color Compan
It is a product name made by y.

The summary of the present invention and its embodiments are summarized below. 1. A. On an exposed surface of a substrate consisting of multiple layers of alternating layers of inorganic dielectric material and layers of thick film conductor,
Containing at least 25% by weight of SiO ₂ and having a softening point below the maximum firing temperature of step (3) below,
Applying a layer of thick film dielectric paste containing finely divided particles of amorphous glass, B. The thick film dielectric layer of step A is selected from (1) Ag, alloys and mixtures of Ag with small amounts of Pd and / or Pt and mixtures thereof, with a maximum particle size of 20 microns, at least 0.1 m ² / g. -Containing metal having a surface area of (2) P
Glass containing at least two metal oxides selected from bO, B ₂ O ₃ , SiO ₂ and Bi ₂ O ₃ and up to 45% by weight selected from oxides of alkali metals, alkaline earth metals, transition metals and mixtures thereof. 15 consisting of modifier
Amorphous glass binder having a dilatometer softening point of 0 to 800 ° C., (3) containing fine particles of an anti-sintering agent selected from oxides of ruthenium and rhodium, mixtures thereof and precursors, and thickness A patterned layer of membrane conductor paste is applied, provided that the amount of sintering inhibitor relative to the amount of conductive metal is within the range connecting points A to D in FIG. 1, and (1) above. , (2) and (3)
Are dispersed in an organic medium; and C.I. The layers to which the thick film dielectric paste and the thick film conductive paste are applied are co-fired in air to volatilize the organic medium from both layers, soften the glass binder and sinter the metal particles in the thick film conductor layer, and thick film. A method for manufacturing a multi-layer electronic circuit comprising continuous steps of densifying glass in a dielectric layer. 2. The method of claim 1 wherein the glass in the thick film dielectric layer is crystalline at a temperature above the softening point of the glass binder in the thick film conductive layer. 3. The method according to item 1 above, wherein the maximum particle size of the silver-containing particles is 10 microns. 4. The method according to item 1 above, wherein the glass in the thick film conductor paste has a dilatometer softening point of 200 to 600 ° C. 5. The method according to item 1 above, wherein the binder in the thick film conductor paste is selected from lead borosilicate, bismuth borosilicate, bismuth lead borosilicate, bismuth borate, lead bismuth borate, lead bismuth silicate glass and mixtures thereof. 6. The method according to item 1 above, wherein the sintering inhibitor is copper bismuth ruthenate. 7. The method according to item 1 above, wherein the sintering inhibitor is RuO ₂ . 8. The method according to item 1 above, wherein the sintering inhibitor is ruthenium resinate. 9. The method according to item 1, wherein the sintering inhibitor is rhodium resinate. 10. The method according to item 1, wherein the dielectric glass remains amorphous upon firing. 11. The method according to item 1, wherein the glass binder in the conductive layer remains amorphous upon firing.

[Brief description of drawings]

FIG. 1 is a diagram showing a ratio of a sintering inhibitor required for a silver-containing conductive metal in a thick film conductive layer.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location H01L 27/01 301 H05K 1/09 Z 6921-4E

Claims (1)

[Claims] 1. A. The exposed surface of a substrate consisting of a plurality of alternating layers of inorganic dielectric material and layers of thick film conductors contains at least 25% by weight of SiO ₂ and the step (3) below Applying a layer of thick film dielectric paste containing finely divided particles of amorphous glass having a softening point below the maximum firing temperature, B. The thick film dielectric layer of step A is selected from (1) Ag, alloys and mixtures of Ag with small amounts of Pd and / or Pt and mixtures thereof, with a maximum particle size of 20 microns, at least 0.1 m ² / g. -Containing metal having a surface area of (2) P
Glass containing at least two metal oxides selected from bO, B ₂ O ₃ , SiO ₂ and Bi ₂ O ₃ and up to 45% by weight selected from oxides of alkali metals, alkaline earth metals, transition metals and mixtures thereof. 15 consisting of modifier
Amorphous glass binder having a dilatometer softening point of 0 to 800 ° C., (3) containing fine particles of an anti-sintering agent selected from oxides of ruthenium and rhodium, mixtures thereof and precursors, and thickness A patterned layer of membrane conductor paste is applied, provided that the amount of sintering inhibitor relative to the amount of conductive metal is within the range connecting points A to D in FIG. 1, and (1) above. , (2) and (3)
Are dispersed in an organic medium; and C.I. The layers to which the thick film dielectric paste and the thick film conductive paste are applied are co-fired in air to volatilize the organic medium from both layers, soften the glass binder and sinter the metal particles in the thick film conductor layer, and thick film. A method of manufacturing a multilayer electronic circuit comprising successive steps of densifying glass in a dielectric layer.